- Enantiodivergent Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols by Dipeptide-Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction
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A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide-phosphonium salt-catalyzed Atherton–Todd (A-T) reaction. This flexible approach led to both R- and S-enantiomers by fine-tuning of bifunctional phosphonium with excellent selectivity factors (s) of up to 1057 and 525, respectively. The potential of newly synthesized O-phosphorylated biaryl diols was illustrated by the synthesis of axially chiral organophosphorus compounds. Mechanistic investigations suggest that the bifunctional phosphonium halide catalyst differentiates between the in-situ-generated P-species in the A-T process, mainly involving phosphoryl chloride and phosphoric anhydride, thus leading to highly enantiodivergent O-phosphorylation reactions. Furthermore hydrogen bonding interactions between the catalysts and phosphorus molecules were crucial in asymmetric induction.
- Chen, Yuan,Fang, Siqiang,Pan, Jianke,Ren, Xiaoyu,Tan, Jian-Ping,Wang, Tianli,Zhang, Hongkui
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p. 14921 - 14930
(2021/05/10)
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- Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki-Miyaura Cross-coupling
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A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki-Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. A series of axially chiral biaryl monophosphine oxides were obtained in good yields and with high enantioselectivities. The practicability of this reaction was validated in the straightforward synthesis of axially chiral biaryl monophosphine ligand and demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations of the product make it as a platform molecule for synthesis of other chiral biaryl phosphines.
- Ji, Wangqin,Wu, Hai-Hong,Zhang, Junliang
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p. 1548 - 1554
(2020/02/04)
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- Optically active phosphine derivative having at least two vinyl groups, polymer produced using the same as monomer, and transition metal complexes of these
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A 2′-diarylphosphino-1,1′-biphenylen-2-yloxy(6,6′-divinyl-1,1′-binaphthalene-2,2′-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): wherein Ar is an optionally substituted phenyl or naphthyl; R1and R2
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- P/O ligand systems: Facile synthesis, structure, and catalytic tests of 2′-phosphanyl-1,1′-bipheny 1-2-ols and 2′-phosphanyl-1,1′-binaphthyl-2-ols
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A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-l,1′-binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveal the presence of P...H-O bridging bonds in the more basic /BuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearance of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanylphenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands. WILEY-VCH Verlag GmbH, 1997.
- Kadyrov, Renat,Heinicke, Joachim,Kindermann, Markus K.,Heller, Detlef,Fischer, Christine,Selke, Ruediger,Fischer, Axel K.,Jones, Peter G.
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p. 1663 - 1670
(2007/10/03)
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- Phosphine compound, complex containing the phosphine compound as ligand, process for producing optically active aldehyde using the phosphine compound or the complex, and 4-[(R)-1'-formylethyl]azetidin-2-one derivatives
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A phosphine compound represented by one of the formulas: STR1 wherein R1 and R2, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a halogen atom or a lower alkyl group or taken together form a divalent hydrocarbon group; and R3 and R4, which may be the same or different, each represent a lower alkyl group, a phenyl group or a phenyl group substituted with a halogen atom, a lower alkyl group or a lower alkoxy group or taken together form a divalent hydrocarbon group, and wherein R6 and R6' which may be the same or different, each represent a hydrogen atom, a lower alkyl group or a lower alkoxy group; R5, R5', R11 and R11' which may be the same or different, each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; or a pair of R5 and R6 or a pair of R5' and R6' may form a ring; R7 and R8, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a lower alkyl group, a halogen atom or a lower alkoxy group; and R9 and R10, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a lower alkyl group, a lower alkoxy group or a halogen atom; or R9 and R10 may be taken together to form a divalent hydrocarbon group.
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- Process for producing optically active aldehydes
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Disclosed herein is a process for producing an optically active aldehyde represented by the following formula (2):, , OHC-CH(CH3)-Q (2), , wherein Q means a halogen atom, lower alkyl group, phthalimide group, lower alkylcarbonyloxy group, cyano group, carboxyl group, lower alkyloxycarbonyl group, lower alkoxy group, lower alkylcarbonyl group, acetylamino group, benzoylamino group, monoalkylamino group, dialkylamino group, benzoyl group, phenyl group which may be substituted by a halogen atom, lower alkyl group or lower alkoxy group, or naphthyl group which may be substituted by a halogen atom, lower alkyl group or lower alkoxy group, which comprises hydroformylating a vinyl compound represented by the following formula (1):, , CH2=CH-Q (1), , wherein Q has the same meaning as defined above, using a specific rhodium-phosphine complex as a catalyst. According to the process, optically active aldehydes which require much labor and time to synthesize, and are expensive can be produced at a high yield and a low cost by a simple process under mild conditions.
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- Optically active tertiary phosphine compound and transition metal complex using the same as ligand
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A phosphine compound represented by formula (I): STR1 wherein Ph represents a phenyl group; and R represents a lower alkyl group or --OR1, wherein R1 represents a hydrogen atom, a cycloalkyl group having from 5 to 7 carbon atoms, or
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